TWI535084B - Thin film fabrication of rubber material with piezoelectric characteristics - Google Patents

Description

Rubber material film structure and manufacturing method with piezoelectric characteristics

The invention relates to a film structure and a manufacturing method of a rubber material with piezoelectric characteristics, in particular to a film structure of a rubber material with piezoelectric properties developed by polymer casting, multi-layer stacking, surface modification, and micro-plasma process. .

In the prior art, in order to prepare the desired porous structure, most of the ferroelectric electrets utilize improved foaming and film forming techniques to introduce gas into the molten polymer to produce bubbles of about 10 microns in size. The plane direction is stretched to produce an elliptical hole structure. Unfortunately, the geometry and spatial distribution of the hole structures generated by these processes are random and difficult to control for individual holes. In addition, these process steps are not compatible with traditional MEMS processes, so that they will encounter great challenges in integration and application.

U.S. Patent No. 8,217,381, entitled "Controlled Buckling Structures in Semiconductor Interconnects and Nanomembranes for Stretchable Electronics." This patent discloses "the present invention provides components that are flexible and selectively printable, such as semiconductor and electronic circuits, that are stretched, compressed, bent or otherwise deformed, and related fabrications or adjustments. The method of the stretchable element can provide good performance. For some applications, the preferred stretchable semiconductors and electronic circuits are flexible. In addition to flexibility, it is more likely to be able to extend, bend, or otherwise deform significantly along one or more axes. Additionally, the stretchable semiconductor and electronic circuits of the present invention are suitable for a wide range of device configurations to provide fully flexible electronic and optoelectronic devices. 』

Referring to FIGS. 8A and 8C, 8B and 8D, a schematic diagram of a method for forming a smooth wavy elastic substrate is disclosed in US Pat. No. 8,217,381. U.S. Patent No. 8,217,381 forms a schematic view of each step of forming a smooth wavy elastic substrate. As shown, the non-isotropic 矽100 etch provides a substrate 20 having sharp edges 24 (shown in Figure 8B). In the sharp edge 24 of the substrate 20 via a deposited photoresist (PR), the photoresist fills the valleys with sharp edges. A resilient stamp 34 is cast to support the substrate 20. The imprint 34 has a recess with sharp edges. A second elastic print 36 is cast onto the imprint 34 to create a stamp having sharp edge crests. Imprint 36 is embossed with Su-8 50 and cured. The photoresist 26 fills the valleys of the Su-8 50 with sharp edges. The elastic substrate 30 is cast to support the Su-8 50, which has a smooth trough. After the substrate 30 is removed, a wavy and smooth surface 32 is displayed. Furthermore, it is disclosed in the independent scope of the patent of US Pat. No. 8,217,381: a two-dimensional stretchable and flexible device comprising: an elastic substrate having a contact surface; an interconnecting portion having a first end, a first a second end portion and a central portion joined to the contact surface of the elastic substrate, the second end portion being bonded to a contact surface of the elastic substrate, the first end portion and the second end portion Between the first end and the second end facing the other This movement produces a curve with a physical separation between the contact surface of the elastic substrate and the central portion of the interconnect, the maximum distance of the physical separation being greater than or equal to 100 nm and less than or equal to 1 mm; the first end connection To a first contact pad, the second end is connected to a second contact pad, wherein the plurality of contact pads are substantially flat for receiving the device component, and the contact pad is bonded to the substrate; When the contact pads are moved relative to each other, the interconnects are electrically connected to the first contact pads and the second contact pads, and the central portion having the curve can cause the device to expand and contract and flex when the electrical connections are maintained.

In the above-mentioned U.S. Patent No. 8,217,381, the technical application discloses how to form a smooth undulating elastic substrate and a two-dimensional stretchable and flexible device; Surface modification and micro-plasma process development of a piezoelectric material film structure with piezoelectric properties is still not complete. Therefore, how to design the above-mentioned rubber material film structure with piezoelectric characteristics will be an important subject for those familiar with the art.

The advantages and spirit of the present invention will be further understood from the following detailed description of the invention.

The main object of the present invention is to provide a film structure and a manufacturing method of a rubber material having piezoelectric properties. The invention has been developed using polymer casting, multilayer stacking, surface modification, and micro-plasma processes. In order to achieve the required electromechanical sensing sensitivity, a dimethyloxane structure containing micropores was designed and fabricated, and bipolar charges were placed on the upper and lower surfaces inside the holes, and the paired charges implanted had electric dipoles. Features that produce a variety of electromechanical sensing relationships.

A film structure of a rubber material having piezoelectric properties, comprising at least: a first electrode layer having a lower surface; a first solid layer of polydimethylsiloxane (PDMS) having an upper surface and a lower surface a surface, the upper surface of the first layer of the first dimethyl oxyalkylene and the lower surface of the first electrode layer are opposite to each other; a first dimethyl methoxy siloxane hole layer having an upper surface a surface and a lower surface, the upper surface of the first dimethyloxane hole layer and the lower surface of the first dimethyl methoxyalkane solid layer are opposite to each other; a bottom dimethyl methoxy oxane a solid layer having an upper surface and a lower surface, the upper surface of the bottom layer of the bottom dimethyl siloxane and the lower surface of the first dimethyl siloxane oxide layer being opposite to each other; The second electrode layer has an upper surface, and the upper surface of the second electrode layer and the lower surface of the bottom solid layer of dimethyl methoxyoxane are opposite to each other.

A method for manufacturing a film structure of a rubber material having piezoelectric properties, comprising the steps of: (1) preparing a first master mold, and forming a solid layer of the first dimethyloxane by using a curing and stripping procedure; a first dimethyloxane hole layer having a top surface and a lower surface, the first dimethyl azide hole layer having an upper surface and a lower surface, The upper surface of the monodimethyl siloxane buffer layer and the lower surface of the first solid layer of dimethyl methoxyalkane are opposite to each other; (2) providing a bottom dimethyl siloxane layer, the bottom The dimethyl siloxane layer has an upper surface and a lower surface, and the upper surface of the bottom dimethyl siloxane layer and the lower surface of the first dimethyl siloxane oxide layer are opposite to each other; And (3) providing a first electrode layer and a second electrode layer, the first electrode layer having a lower surface, And the second electrode layer has an upper surface such that the lower surface of the first electrode layer and the upper surface of the first solid layer of dimethyloxysiloxane become opposite to each other, and the upper surface of the second electrode layer The lower surface of the surface and the solid layer of the bottom dimethyl methoxyoxane are opposite to each other.

Conventional technology:

100‧‧‧矽

24‧‧‧ sharp edges

20‧‧‧Substrate

34‧‧‧Elastic imprint

36‧‧‧Second elastic mark

50‧‧‧Su-8

26‧‧‧Light resistance

30‧‧‧elastic substrate

32‧‧‧Wave and smooth surface

this invention:

(1)~(18)‧‧‧Step number

1‧‧‧Metal material film structure

11‧‧‧First electrode layer

112‧‧‧ lower surface

116‧‧‧First elastic gold film layer

1162‧‧‧ lower surface

117‧‧‧First 3-thiol trimethoxydecane bonding layer

1171‧‧‧ upper surface

1172‧‧‧ lower surface

12‧‧‧First dimethyl oxane solid layer

121‧‧‧ upper surface

122‧‧‧ lower surface

13‧‧‧First dimethyloxane hole layer

131‧‧‧ upper surface

132‧‧‧ lower surface

14‧‧‧Second dimethyl oxa oxide solid layer

141‧‧‧ upper surface

142‧‧‧ lower surface

15‧‧‧Second dimethyloxane hole layer

151‧‧‧ upper surface

152‧‧‧ lower surface

16‧‧‧Bottom dimethyl oxa oxide solid layer

161‧‧‧ upper surface

162‧‧‧ lower surface

17‧‧‧Second electrode layer

171‧‧‧ upper surface

176‧‧‧Second elastic gold film layer

1761‧‧‧ upper surface

177‧‧‧Second 3-thiol-trimethoxydecane bonding layer

1771‧‧‧ upper surface

1772‧‧‧ lower surface

W1‧‧‧ first wafer

W11‧‧‧ upper surface

M1‧‧‧ first female model

R1‧‧‧First SU-8 3050 photoresist layer

X1‧‧‧ first perfluorooctyltrichloromethane layer

X11‧‧‧ upper surface

P1‧‧‧ first dimethyloxane layer

P11‧‧‧ upper surface

X2‧‧‧Second perfluorooctyltrichloromethane layer

X21‧‧‧ upper surface

P5‧‧‧ dimethyloxane layer

P5'‧‧‧ first dimethyl decane carrier layer

S1‧‧‧ first structure

W2‧‧‧second silicon wafer

W21‧‧‧ upper surface

M2‧‧‧ second mother model

R2‧‧‧Second SU-8 3050 photoresist layer

X3‧‧‧ third perfluorooctyltrichloromethane layer

P2‧‧‧Second dimethyloxane layer

P21‧‧‧ upper surface

X3‧‧‧ third perfluorooctyltrichloromethane layer

X31‧‧‧ upper surface

P3‧‧‧ bottom dimethyloxane layer

P31‧‧‧ upper surface

S2‧‧‧ second structure

H‧‧‧Internal holes

T‧‧‧ channel

XA5‧‧‧Perfluorooctyltriethoxysilane adhesive layer

PT‧‧‧Teflon layer

1 is a schematic exploded view of a preferred embodiment of a film structure of a rubber material having piezoelectric characteristics; and FIG. 2A is a preferred embodiment of a film structure of a rubber material having piezoelectric characteristics of the present invention. A schematic diagram of an electrode layer decomposition; a second diagram is a schematic view of a second electrode layer of a preferred embodiment of the piezoelectric material film structure of the present invention; and a third figure is a rubber material having piezoelectric characteristics of the present invention. A flow chart of a preferred embodiment of a method of film structure; and FIGS. 4A through 4R are formed by each step of a preferred embodiment of the method for fabricating a film structure of a piezoelectric material of the present invention. Schematic diagram of the structure; the fifth A is a schematic diagram of the independent pores of the inner hole of the multi-layer casting microstructure of the film structure of the rubber material of the present invention; the fifth B is the film structure of the rubber material having the piezoelectric property of the invention A schematic view of a hole connecting the internal passages of the multi-layer casting microstructure; the fifth C is a multi-layer casting microstructure of the piezoelectric material film structure of the present invention having the pores connected in a checkerboard shape Schematic diagram 6A and 6B are schematic diagrams showing the working principle of a film structure of a rubber material having piezoelectric characteristics of the present invention; and a seventh diagram showing a simple model of a film structure of a rubber material having piezoelectric characteristics of the present invention; A diagram of a method for forming a smooth undulating elastic substrate is shown in U.S. Patent No. 8,217,381, the entire disclosure of which is incorporated herein by reference. , 217, 381 form a structural schematic diagram of each step of forming a smooth wavy elastic substrate.

The invention relates to a film structure of a rubber material with piezoelectric properties, which is developed by polymer casting, multi-layer stacking, surface modification, and micro-plasma process. In order to achieve the required electromechanical sensing sensitivity, a dimethyl methoxy hydride (PDMS) structure containing micropores was designed and fabricated, and bipolar charges were placed on the upper and lower surfaces inside the holes, and the paired charges were electrically charged. Dipole characteristics can produce a variety of electromechanical sensing relationships. In the initial verification of the prototype, holes of various geometric shapes were produced in the dimethyl methoxide (PDMS) film structure through the process, and a thin layer of polytetrafluoroethylene (polytetrafluoro) was applied to the surface of the hole. PTFE) polymer material to capture and stabilize the charge that is implanted on the surface of the hole. When an applied electric field is connected across the dimethyl methoxide (PDMS) film and rises to 27 MV/m, the air inside the hole begins to be ionized and accelerated, and the collision produces a large amount of bipolar charge, which is guided by the electric field. Implant the surface in the opposite direction. Porous rubber material The effective elastic modulus (E) of the film is less than 500 kPa, and the piezoelectric coefficient (d33) exhibited by the dipole formed by the charge implantation can be higher than 1000 pC/N or more, compared with the conventional piezoelectric polymer material ( Such as polyvinylidene fluoride, PVDF) is more than 30 times higher. In addition, the piezoelectric properties of the rubber material film can be adjusted by changing the geometric parameters of the internal porous structure, and have a high potential to be made into a soft material with high electromechanical sensing sensitivity, which fully satisfies various sensors and actuations. Requirements for related applications such as instrumentation, biological monitoring, and energy conversion.

Please refer to FIG. 6A and FIG. 6B, which are schematic diagrams showing the working principle of a piezoelectric material film structure with piezoelectric characteristics according to the present invention, wherein FIG. 6A is a structure of a ferroelectric electret, sixth. Figure B shows the generation of piezoelectric characteristics after stress deformation. The paired charges implanted are equivalent to electric dipoles and can produce a variety of electromechanical sensing relationships, and the charge implantation procedure is performed between parallel plate electrodes. Under this geometry, the conditions for air dissociation are usually predicted by Paschen's law, but for small pitches of micron size, the predicted values obtained will have significant errors. For micron-scale gaps, in general, the electric field required to cause dissociation will be higher than the value predicted by Paschen's law. Once the applied voltage exceeds the dissociation threshold, a micro-plasma discharge phenomenon occurs inside the hole and stops extinguishing at a later time because the bipolar charge has been deposited on the upper and lower opposing surfaces of the internal structure, and the induced electric field cancels the effect of the applied electric field. The porous rubber material structure in which the charge has been deposited has a high degree of softness and a high degree of polarization. When the force is deformed, the electric dipole moment in the structure also changes, thereby producing the desired piezoelectric characteristics. As shown in Fig. B, when an external force is applied to the porous rubber material structure in which the electric charge has been deposited, it is expected that the thickness thereof will change. In addition, The induced charge density at the upper and lower electrodes also changes.

Please refer to the seventh figure, which is a simplified model diagram of the film structure of the rubber material with piezoelectric characteristics of the present invention. The structure includes upper and lower electrodes, and the solid and hole structure layers are sandwiched between the two electrodes. For a structure with n-layer holes and n+1 layer entities, the internal electric field in the solid layer (E1) and the hole layer (E2) can be estimated by Gauss'law.

Please refer to the first figure, which is an exploded perspective view of a preferred embodiment of a film structure of a rubber material having piezoelectric characteristics. The piezoelectric material film structure 1 having piezoelectric characteristics comprises: a first electrode layer 11 having a lower surface 112; a first solid layer 12 of polydimethylsiloxane (PDMS) having an upper surface 121 and the lower surface 122, the upper surface 121 of the solid layer 12 of the first dimethyl siloxane and the lower surface 112 of the first electrode layer 11 are opposite to each other; a first dimethyl oxime The alkane layer 13 has an upper surface 131 and a lower surface 132. The upper surface 131 of the first dimethyloxane hole layer 13 and the lower surface 122 of the first dimethyl siloxane solid layer 12 Opposite to each other; a second dimethyl siloxane solid layer 14 having an upper surface 141 and a lower surface 142, the upper surface 141 of the second dimethyl siloxane solid layer 14 The lower surface 132 of the first dimethyl fluorene oxide hole layer 13 is opposite to each other; a second dimethyl fluorene oxide hole layer 15 has an upper surface 151 and a lower surface 152, the second The upper surface 151 of the dimethyloxane hole layer 15 and the second dimethyl The lower surface 142 of the bismuth oxyalkylene solid layer 14 is opposite to each other; a bottom dimethyl oxyalkylene solid layer 16 having an upper surface 161 and a lower surface 162, the bottom dimethyl methoxy oxane The upper surface 161 of the solid layer 16 and the lower surface 152 of the second dimethyloxane hole layer 15 are opposite to each other; and a second electrode layer 17 having an upper surface 171, the second The upper surface 171 of the electrode layer 17 and the lower surface 162 of the bottom dimethyl siloxane solid layer 16 are opposite to each other.

Please refer to FIG. 2A and FIG. 2B, which are schematic diagrams showing the first electrode layer of the preferred embodiment of the piezoelectric material film structure of the present invention, and the piezoelectric material film structure of the present invention having piezoelectric characteristics. A schematic exploded view of a second electrode layer of the preferred embodiment. As shown in FIG. 2A, the first electrode layer 11 includes: a first elastic gold film layer 116 having a lower surface 1162; and a first 3-thiol trimethoxy decane (3). a mercaptopropyltrimethoxysilane (MPTMS) bonding layer 117 having an upper surface 1171 and a lower surface 1172, the lower surface 1162 of the first elastic gold film layer 116 and the first 3-thiol trimethoxy group The upper surface 1171 of the decane bonding layer 117 is opposite to each other, wherein the lower surface 1172 of the first 3-thiol trimethoxydecane bonding layer 117 and the lower surface 112 of the first electrode layer 11 One is the same side. As shown in FIG. 2B, the second electrode layer 17 includes: a second 3-thiol-trimethoxydecane bonding layer 177 having an upper surface 1771 and a lower surface 1772; and a second elastic gold film layer. 176, having an upper surface 1761, the lower surface 1772 of the second 3-thiol-trimethoxydecane bonding layer 177 and the upper surface 1761 of the second elastic gold film layer 176 are opposite to each other The upper surface 1771 of the second 3-thiol trimethoxydecane bonding layer 177 is identical to the upper surface 1761 of the second electrode layer 17.

Please refer to the third figure, which is a flow chart of a preferred embodiment of the method for fabricating a film structure of a rubber material having piezoelectric characteristics, and also refers to the fourth to fourth R drawings of the present invention. A schematic view of the structure formed by each step of the preferred embodiment of the piezoelectric material film structure of the piezoelectric property. As shown in the figure, the method comprises the following steps: (1) defining a pattern (a portion having a recess and a protrusion in the figure, which is a schematic portion of the pattern) on an upper surface W11 of a first wafer W1. a first master mold M1 is prepared, that is, a first SU-8 3050 photoresist layer R1 having a thickness of about 50 μm is coated on the upper surface W11 of the first tantalum wafer W1 according to the pattern to form the first mother mold M1. The first master mold M1 is as shown in FIG. 4A; (2) the first master mold M1 is placed in a vacuum vessel (not shown) and coated with a first perfluorooctyltrichloromethane ( 1H, 1H, 2H, 2H-perfluorooctyl-trichlorosilane layer X1 on the first SU-8 3050 photoresist layer R1 and the upper surface W11 of the first germanium wafer W1 for surface decane reforming, which will facilitate subsequent Stripping release, as shown in FIG. 4B; (3) coating a first dimethyl siloxane layer P1 having a thickness of about 100 μm on one of the first perfluorooctyltrichloromethane layers X1 Surface X11, followed by baking at 85 ° C for one hour, as shown in FIG. 4C; (4) coating a second perfluorooctane on the upper surface P11 of one of the cured first dimethyl siloxane layer P1 Trichlorodecane layer X2 for surface decane Modification, as the fourth D in FIG. (5) coating a surface of the second perfluorooctyltrichloromethane layer X2 on the upper surface X21 with a dimethyl oxa oxide layer P5 having a thickness of about 2 mm to serve as a first dimethyloxane a carrier layer P5', as shown in FIG. 4E; (6) utilizing the chemical characteristics of the first perfluorooctyltrichloromethane layer X1, the first dimethyloxane carrier from top to bottom a layer P5', a second perfluorooctyltrichloromethane layer X2, a first dimethyloxonane solid layer 12 and a first dimethyloxonium oxide layer 13 of a first dimethyloxane layer P1 is peeled off from the first SU-8 3050 photoresist layer R1 including the top-down and the first master mold M1 of the first germanium wafer W1, thereby forming a first structure S1, the first structure S1 includes a first dimethyl decane carrier layer P5', a second perfluorooctyltrichloromethane layer X2 and a first dimethyl decane layer P1 (containing a first dimethyl oxime) from top to bottom. The solid layer of alkane 12 and the first dimethyloxane hole layer 13) are as shown in the fourth F diagram; (7) define another pattern (the portion having a concave portion and a convex portion in the drawing, which is a schematic diagram of the figure) Prepared on the upper surface W21 of one of the second silicon wafers W2 to prepare And forming a second female mold M2, that is, coating a second SU-8 3050 photoresist layer R2 having a thickness of about 50 μm on the upper surface W21 of the second germanium wafer W2 according to the pattern to form the second female M2, as shown in the fourth G; (8) placing the second master M2 in a vacuum vessel (not shown) and coating a third perfluorooctyltrichloromethane (1H, 1H) , 2H, 2H-perfluorooctyl-trichlorosilane) layer X3 on the second SU-8 3050 photoresist layer R2 and the upper surface W21 of the second tantalum wafer W2 for surface decane reforming, which will facilitate subsequent stripping Mode, such as a fourth H-graph is shown; (9) a second dimethyl siloxane layer P2 having a thickness of about 100 μm is coated on the upper surface X31 of the third perfluorooctyltrichloromethane layer X3, followed by 85 Baking at ° C for one hour, as shown in FIG. 4; (10) on the lower surface 132 of the first dimethyl fluorene oxide hole layer 13 of the first dimethyl siloxane layer P1 of the first structure S1. Surface-plasma treatment with the upper surface P21 of the second dimethyl siloxane layer P2, and then having the first PDMS carrier layer P5', the second perfluorooctyltrichloromethane layer X2 and the first dimethyl group The first structure of the siloxane layer P1 is superposed on the second dimethyl siloxane layer P2 and baked at 85 ° C for at least one hour to bond the first dimethyl siloxane layer P1 with a second dimethyl azide layer P2, as shown in the fourth J; (11) utilizing the chemical properties of the third perfluorooctyltrichloromethane layer X3, the second dimethyl oxa oxide-containing solid The layer 14 and the second dimethyl azide layer P2 of the second dimethyl siloxane layer 15 are from a second SU-8 3050 photoresist layer R2 and a second germanium wafer from top to bottom. The second female mold M2 of W2 is peeled off and released, as shown in the fourth K diagram. (12) providing a bottom dimethyl siloxane layer P3 having a thickness of about 100 μm as shown in the fourth L; (13) an upper surface P31 and a second surface of the bottom dimethyl siloxane layer P3; The surface 152 of the second dimethyl fluorene oxide hole layer 15 of the dimethyl siloxane layer P2 is subjected to surface plasma treatment, and the second dimethyl siloxane layer P2 is laminated and bonded to the bottom dimethyl group. Above the siloxane layer P3 and baked at 85 ° C for at least one hour to bind the second dimethyl The base oxyalkylene layer P2 and the bottom dimethyl siloxane layer P3 further form a first dimethyl decane carrier layer P5' and a second perfluorooctyltrichloromethane layer X2 from top to bottom. a first dimethyl decane layer P1 comprising a first dimethyl oxyalkylene solid layer 12 and a first dimethyl methoxy siloxane hole layer 13 and a second dimethyl oxa oxide solid layer 14 a second structure S2 of the second dimethyloxane layer P2 of the second dimethyloxane hole layer 15 and one of the bottom dimethyl azide layer P3, as shown in the fourth M; (14) A plurality of solutions of perfluorooctyltriethoxysilane are introduced into the plurality of internal pores H and channels T of the second structure S2 to form a perfluorooctyltriethoxydecane adhesion layer XA5 in each of the holes H and channels. Above T, as shown in the fourth N; (15) introducing a plurality of polytetra-fluoroethylene (Teflon, PTFE for short) solutions into the plurality of internal holes H and channels T of the second structure S2, Forming a polytetrafluoroethylene layer PT on the pores H and the channel T on the perfluorooctyltriethoxydecane adhesion layer XA5, wherein the polytetrafluoroethylene polymer material, The polymer film deposited on the PTFE layer of the PTFE layer is as shown in FIG. 4; (16) using the chemical property of the second perfluorooctyltrichloromethane layer X2, the first dimethyl hydrazine can be used. The oxyalkylene carrier layer P5' is separated from the second perfluorooctyltrichloromethane layer X2 to complete the stacked first dimethyloxane layer P1, the second dimethyloxane layer P2 and the bottom dimethyl oxime The alkane layer P3 is due to the bonding strength between the surface of the dimethyloxane being greater than the bonding strength between the surfaces after the decaneization treatment, as shown in the fourth P diagram; (17) in the first dimethyl anthracene The upper surface 121 of the alkane layer P1 and the lower surface 162 of the bottom dimethyl azide layer P3 form a first 3-thiol-trimethoxydecane adhesion layer. 117 and a second 3-thiol-trimethoxydecane adhesion layer 177, as shown in the fourth Q; (18) forming a first elastic gold film layer 116, respectively, in the first 3-sulfur An alcohol-based trimethoxydecane adhesion layer 117 and a second elastic gold film layer 176 are bonded to the second 3-thiol-trimethoxydecane adhesion layer 177, wherein the first electrode layer 11 comprises a first 3-sulfur An alcohol-based trimethoxydecane adhesion layer 117 and the first elastic gold film 116, the second electrode layer 17 includes a second 3-thiol-trimethoxydecane adhesion layer 177 and the second elastic gold film 176, and The upper surface 1171 of the 3-thiol-trimethoxydecane adhesion layer 117 and the lower surface 1162 of the first elastic gold film 116 are opposite to each other, and the second 3-thiol-trimethoxydecane adhesion layer 177 is under The surface 1772 and the upper surface 1761 of the second elastic gold film 176 are opposite to each other as shown in the fourth R diagram.

Please refer to FIGS. 5A to 5C, which are schematic diagrams of independent pores of the inner hole of the multi-layer casting microstructure of the film structure of the rubber material with piezoelectric characteristics of the present invention, and the multilayer structure of the film structure of the rubber material with piezoelectric characteristics of the present invention. Schematic diagram of the hole connecting the internal passage of the cast microstructure and the hole in the multi-layer casting microstructure of the film structure of the rubber material of the present invention are connected as a checkerboard pattern, and the inside of the fifth and fifth C drawings The pore structures are connected to each other, and both are open and connected to the external atmosphere, and can provide a surface modification step of the subsequent internal pores, and the fifth C is a columnar structure of dimethyloxane. Furthermore, the fifth A diagram and the fifth C diagram are positive and negative in the definition of the reticle, so after the overmolding, the independent aperture of the fifth A diagram will become the columnar structure of the fifth C diagram. Methyl decane. As the surface plasma treatment mentioned in the step (10), a hand-held surface corona processor (BD-20AC, Electro-Technic Products) is used, which functions to ionize the surrounding air to generate a local plasma. The surface of the treated sample is caused to irreversibly combine. The plasma density of this corona processor is set to a relatively low level to produce a more stable and gentle plasma that prevents sample damage and burnout. The linear electrode of the corona processor is placed about 3 mm above the surface of the sample to be treated, and is continuously swept back and forth for about 30 seconds to one minute. The length of the treatment time is adjusted according to the surface size of the sample. The surface treated samples were stacked on top of each other and baked at 85 ° C for at least one hour to complete irreversible binding. In the preliminary test, the multi-layer stack structure was a two-layered void layer plus three solid layers. The overall dimethyl fluorene oxide film structure had a thickness of about 300 μm and an area of about 3 cm × 3 cm. As shown in the fifth A diagram, the size of the internal holes is 50 × 50 × 50 μm ³ , and the distance between the holes is 50 μm. In addition to the independent pore structure, the mutually connected pore structure is prepared as described above. The fifth B is a schematic diagram of the geometry of the hole structure that is connected. The adjacent holes are connected by a channel having a width of 20 μm and a depth of 50 μm, so that the modification and modification of the surface of the hole is easier. The fifth C picture shows the structural design used today. The holes are connected to a checkerboard-like structure, and the width and depth are 50 μm. The rubber material structure is a columnar structure with a length, width and depth of 50 μm. The overall film structure was supported, and as shown in Figs. 5A and 5B, the size of the internal holes was 50 × 50 × 50 μm ³ , and the distance between the holes was 50 μm. This design provides a large charge storage area that will effectively increase the amount of charge stored. It is generally believed that a semi-latticated polymer has a strong ability to capture stored charges and can help improve the piezoelectric properties of the porous rubber material structure. To this end, a PTFE solution (Teflon, DuPont) is filled in the interconnected pore structure, and when the solvent is evaporated, a polymer film having a semi-latticized structure is formed on the surface of the pore, and the thickness thereof is about 1 μm. As shown in the fourth N diagram and the fourth O diagram. After the structure is completed, a gold film is applied to the upper and lower surfaces of the rubber material film as an electrode, and the thickness is about 100 nm, as shown in the fourth Q diagram and the fourth R diagram, and the charge is implanted in a strong electric field. On the inner surface of the structure. In the experiment, when the applied voltage is 8kV, the corresponding electric field strength is about 27 MV/m, which can make the air in the hole begin to ionize. Once the dissociation electric field is reached, the self-extinguishing microplasma discharge phenomenon will occur in each hole at the same time, accompanied by a short-term luminescence phenomenon, while the charge is accelerated and impinged on the surface of each hole. The driving voltage used in the experiment is a triangular wave with an amplitude between 7.5 and 11.5 kV, and the rubber material film structure is repeatedly charged at a frequency lower than 0.5 Hz for 15 minutes while heating the sample to maintain about 100 ° C during charging. The temperature to enhance the charging effect. Once the internal charging is completed, the porous rubber material film becomes a material having excellent elasticity and piezoelectric sensing sensitivity, and can be applied to various energy conversion occasions such as acoustic energy and electric energy, or electric energy and mechanical energy.

Accordingly, the present invention develops a multilayer structure casting, stacking, surface modification, and micro plasma discharge process that can efficiently manufacture and control porous microstructures, enabling rapid fabrication of desired porosity and good Piezoelectric rubber material film with electromechanical sensing characteristics. The paired charges after implantation have the characteristics of electric dipoles, which can produce various electromechanical sensing relationships. The rubber material and related processes are highly compatible with traditional micro-electromechanical processes, so the piezoelectric film process for rubber materials is expected to be smoothly integrated with MEMS. The porous rubber material piezoelectric film has a very low effective modulus (E), and its value is less than 500 kPa, and its piezoelectric coefficient (d ₃₃ ) is as high as 1000 pC N ^-1 or more, which has surpassed the general piezoelectric ceramics. More than three times the level, and far more than thirty times higher than traditional piezoelectric polymers (such as PVDF). The low elastic modulus of the porous rubber material film structure and the high charge density of the polytetrafluoroethylene (PTFE) film can produce very strong piezoelectric characteristics. In addition, the properties of the piezoelectric film of the rubber material can also be controlled by changing the size and distribution of the internal pore structure. As described above, the piezoelectric rubber material film has a very high potential for use in a micro system, and is capable of producing components with high elasticity and high electromechanical sensing sensitivity characteristics, and can satisfy various sensing and energy conversion applications.

Thus, the patent application of the present invention utilizes the inventor's rich experience to design a simple but fully problematic solution to the conventional technology with a very creative concept. Therefore, the function of the patent application of the present invention does meet the patent requirements of novelty and progress.

The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto. It is to be understood that the scope of the present invention is not limited by the spirit and scope of the present invention, and should be considered as a further embodiment of the present invention.

1‧‧‧Metal material film structure

11‧‧‧First electrode layer

112‧‧‧ lower surface

12‧‧‧First dimethyl oxane solid layer

121‧‧‧ upper surface

122‧‧‧ lower surface

13‧‧‧First dimethyloxane hole layer

131‧‧‧ upper surface

132‧‧‧ lower surface

14‧‧‧Second dimethyl oxa oxide solid layer

141‧‧‧ upper surface

142‧‧‧ lower surface

15‧‧‧Second dimethyloxane hole layer

151‧‧‧ upper surface

152‧‧‧ lower surface

16‧‧‧Bottom dimethyl oxa oxide solid layer

161‧‧‧ upper surface

162‧‧‧ lower surface

17‧‧‧Second electrode layer

171‧‧‧ upper surface

Claims (15)

A film structure of a rubber material having piezoelectric properties, comprising at least: a first electrode layer having a lower surface; a first solid layer of polydimethylsiloxane (PDMS) having an upper surface and a lower surface a surface, the upper surface of the first layer of the first dimethyl oxyalkylene and the lower surface of the first electrode layer are opposite to each other; a first dimethyl methoxy siloxane hole layer having an upper surface a surface and a lower surface, the upper surface of the first dimethyloxane hole layer and the lower surface of the first dimethyl methoxyalkane solid layer are opposite to each other; a bottom dimethyl methoxy oxane a solid layer having an upper surface and a lower surface, the upper surface of the bottom layer of the bottom dimethyl siloxane and the lower surface of the first dimethyl siloxane oxide layer being opposite to each other; The second electrode layer has an upper surface, and the upper surface of the second electrode layer and the lower surface of the bottom solid layer of dimethyl methoxyoxane are opposite to each other. The film structure of the rubber material having the piezoelectric property as described in claim 1, further comprising: a solid layer of a second dimethyl siloxane having an upper surface and a lower surface, the second dimethyl group The upper surface of the solid layer of the oxyalkylene and the lower surface of the first dimethyloxane hole layer are opposite to each other; a second dimethyloxane hole layer having an upper surface and a lower surface, the upper surface of the second dimethyl azide hole layer and the second dimethyl siloxane solid layer The lower surfaces are opposite to each other; wherein the lower surface of the second dimethyl azide hole layer and the upper surface of the bottom dimethyl siloxane solid layer are opposite to each other. The film structure of the rubber material having the piezoelectric property according to the first aspect of the invention, wherein the first electrode layer comprises: a first elastic gold film layer having a lower surface; a 3-mereaptopropyltrimethoxysilane (MPTMS) adhesive layer having an upper surface and a lower surface, the lower surface of the first elastic gold film layer and the first 3 The upper surface of the thiol-group trimethoxydecane bonding layer is opposite to each other. The film structure of a rubber material having piezoelectric properties according to claim 3, wherein the lower surface of the first 3-thiol-trimethoxydecane bonding layer and the lower surface of the first electrode layer One is the same side. The film structure of a rubber material having piezoelectric properties according to claim 1, wherein the second electrode layer comprises: a second 3-thiol-trimethoxydecane bonding layer having an upper surface and Look at the surface; and A second elastic gold film layer has an upper surface, and the lower surface of the second 3-thiol-trimethoxydecane bonding layer and the upper surface of the second elastic gold film layer are opposite to each other. The film structure of a rubber material having piezoelectric properties according to claim 5, wherein the upper surface of the second 3-thiol-trimethoxydecane bonding layer and the upper surface of the second electrode layer One is the same side. A method for manufacturing a film structure of a rubber material having piezoelectric properties, comprising the steps of: (1) preparing a first master mold, and forming a solid layer of the first dimethyloxane by using a curing and stripping procedure; a first dimethyloxane hole layer having a top surface and a lower surface, the first dimethyl azide hole layer having an upper surface and a lower surface, The upper surface of the monodimethyl siloxane oxide layer and the lower surface of the first solid layer of dimethyl methoxyalkane are opposite to each other; (2) providing a solid layer of bottom dimethyl methoxy hydride, The bottom dimethyl siloxane solid layer has an upper surface and a lower surface, and the upper surface of the bottom dimethyl siloxane solid layer and the lower surface of the first dimethyl siloxane oxide layer are mutually And (3) providing a first electrode layer and a second electrode layer, the first electrode layer having a lower surface, and the second electrode layer having an upper surface such that the lower surface of the first electrode layer The upper surface of the solid layer of the first dimethyl methoxyoxane becomes mutually The opposite surface, and the upper surface of the second electrode layer and the lower surface of the bottom solid layer of dimethyl siloxane are opposite to each other. The method for manufacturing a film structure of a rubber material having piezoelectric characteristics according to claim 7, wherein the step (1) further comprises the following steps: (11) defining a pattern on one of the first wafers. Surfacely, the first master mold is prepared, that is, a first SU-8 3050 photoresist layer having a thickness of about 50 μm is coated on the upper surface of the first germanium wafer according to the pattern to form a first mother. (12) placing the first master mold in a vacuum vessel and coating a first layer of perfluorooctyltrichlorosilane (1H, 1H, 2H, 2H-perfluorooctyl-trichlorosilane) on the first SU- 8 3050 photoresist layer and the upper surface of the first germanium wafer for surface decane reforming, which will facilitate subsequent stripping and demolding; (13) a first dimethyl siloxane layer having a thickness of 100 μm Coating on one surface of the first perfluorooctyltrichloromethane layer, followed by baking at 85 ° C for one hour; (14) coating the upper surface of one of the cured first dimethyl siloxane layers a second perfluorooctyltrichloromethane layer for surface decanoation modification; (15) a surface of one of the second perfluorooctyltrichloromethane layers coated with a thickness of about 2 mm a dimethyloxane layer as a first dimethyl oxane carrier layer; and (16) a first perfluorooctyltrichloromethane layer, which may be the first two from top to bottom a methyl oxane carrier layer, a second perfluorooctyltrichloromethane layer, a first dimethyl group comprising a first dimethyl methoxyoxane solid layer and a first dimethyl methoxy oxane hole layer The siloxane layer is stripped from the first master mold comprising the first SU-8 3050 photoresist layer from top to bottom and the first ruthenium wafer. The method for manufacturing a film structure of a rubber material having piezoelectric characteristics according to claim 7, wherein the step (1) further comprises the following steps: (1A) preparing a second master mold and utilizing a curing procedure Forming a second solid layer of dimethyl methoxyoxane and a second dimethyl siloxane oxide layer having a top surface and a lower surface, the second dimethyl group The oxane hole layer has an upper surface and a lower surface, and the upper surface of the second dimethyl siloxane oxide layer and the lower surface of the second dimethyl siloxane solid layer are opposite to each other, and a dimethyl methoxy siloxane hole layer is still attached to the second master mold; (1B) the first dimethyl methoxy oxyalkylene solid layer is bonded to the first dimethyl methoxy oxane hole layer a solid layer of bismuth oxyalkylene and a second dimethyloxane hole layer; (1C) using a stripping procedure to separate the second layer of the second dimethyl siloxane from the second dimethyl methoxy hydride hole layer a second master mold; and (1D) joining the lower surface of the second dimethyloxane hole layer to the bottom dimethyl methoxyane solid layer Surface. The method for manufacturing a film structure of a rubber material having piezoelectric characteristics according to claim 9, wherein the step (1A) further comprises the step of: (1A1) defining a pattern on one of the second wafers. Surfacely, a second master mold is prepared, that is, a second SU-8 3050 photoresist layer having a thickness of about 50 μm is coated on the upper surface of the second tantalum wafer according to the pattern to form the second mold. Master model (1A2) placing the completed second master in a vacuum vessel and coating a layer of a third perfluorooctyltrichlorosilane (1H, 1H, 2H, 2H-perfluorooctyl-trichlorosilane) on the second SU -8 3050 photoresist layer and the upper surface of the second germanium wafer for surface decane reforming, which will facilitate subsequent stripping demolding; and (1A3) a second dimethyloxy group with a thickness of 100 μm An alkane layer was coated on the upper surface of one of the third perfluorooctyltrichloromethane layers, followed by baking at 85 ° C for one hour. The method for manufacturing a film structure of a rubber material having piezoelectric properties according to claim 9 , wherein the step (1B) further comprises the step of: (1B1) laying down one of the first dimethyl azide hole layers; The surface is surface-plasma treated with one surface of the second dimethyl siloxane layer, and then has a first dimethyl siloxane carrier layer, a second perfluorooctyl chloroform layer and a first dimethyl group. The first structure of one of the oxyalkylene layers is superposed on the second dimethyl siloxane layer and baked at 85 ° C for at least one hour to bond the first dimethyl siloxane layer with the first Dimethyl siloxane layer. The method for producing a film structure of a rubber material having piezoelectric properties according to claim 9, wherein the step (1C) further comprises the step of: (1C1) utilizing the third perfluorooctyltrichloromethane layer; Chemically characterized, comprising a second dimethyl siloxane layer comprising a solid layer of a second dimethyl methoxyoxane and a second dimethyl siloxane chain layer from a second SU-8 3050 comprising a top to bottom The photoresist layer is peeled off from the second master of the second germanium wafer to release the film. The method for manufacturing a film structure of a rubber material having piezoelectric characteristics according to claim 9, wherein the step (1D) further comprises the step of: (1D1) providing the bottom dimethyl methoxyoxane having a thickness of 100 μm. And (1D2) surface-treating the lower surface of one of the upper surface of the bottom dimethyl azide layer and the second dimethyl siloxane layer of the second dimethyl siloxane layer, Then, the second dimethyl methoxy alkane is laminated on the bottom dimethyl siloxane layer and baked at 85 ° C for at least one hour to bond the second dimethyl siloxane layer with the bottom two a methyl siloxane layer, further comprising a first dimethyl decane carrier layer comprising a top to bottom, a second perfluorooctyltrichloromethane layer, a first dimethyl oxa oxide solid layer and a first dimethyl fluorene oxide layer of the first dimethyl fluorene oxide hole layer, a second dimethyl hydrazine layer containing a second dimethyl methoxy oxyalkylene solid layer and a second dimethyl methoxy oxane hole layer A second structure of one of an oxyalkylene layer and a bottom dimethyl siloxane layer. The method for manufacturing a film structure of a rubber material having piezoelectric characteristics according to claim 13 , wherein the step (1D2) further comprises the following steps: (1D2A), a plurality of drops of perfluorooctyltriethoxydecane The solution is introduced into a plurality of internal pores and channels of the second structure to form a perfluorooctyltriethoxydecane adhesion layer on each of the pores and the channel; and (1D2B) a plurality of polytetrafluoroethylene (polytetra-) A fluoroethylene (commonly known as Teflon, PTFE for short) solution is introduced into a plurality of internal pores and channels of the second structure to form a polytetrafluoroethylene layer on the pores and channels of the perfluorooctyl a polytrifluoroethylene-based polymer material, wherein the polytetrafluoroethylene layer is deposited on the adhesive layer; and (1D2C) first dimethyloxane carrier The layer is separated from the second perfluorooctyltrichloromethane layer to complete the stacked first dimethyloxane layer, the second dimethyloxane layer and the bottom dimethyloxane layer, due to the dimethyl group. The bonding strength between the surface of the oxirane is greater than the bonding strength between the surfaces after the decaneization treatment. The method for manufacturing a film structure of a rubber material having piezoelectric characteristics according to claim 7, wherein the step (3) further comprises the step of: (31) working on one of the first dimethyl siloxane layers; Forming a first 3-thiol-trimethoxydecane adhesion layer and a second 3-thiol-trimethoxydecane adhesion layer on the lower surface of the surface and the bottom dimethyl azide layer; and (32) respectively Forming a first elastic gold film on the first 3-thiol-trimethoxydecane adhesion layer and a second elastic gold film on the second 3-thiol-trimethoxydecane, wherein The first electrode layer includes a first 3-thiol trimethoxydecane adhesive layer and the first elastic gold film, and the second electrode layer includes a second 3-thiol trimethoxydecane adhesive layer and the first electrode layer a second elastic gold film, and the upper surface of one of the first 3-thiol-trimethoxydecane adhesion layer and the lower surface of one of the first elastic gold films are opposite to each other, and the second 3-thiol-trimethoxydecane is adhered One of the lower surface of the layer and one of the upper surfaces of the second elastic gold film are opposite to each other.